Determination of organic micropollutants in rainwater using hollow fiber membrane/liquid-phase microextraction combined with gas chromatography–mass spectrometry

A simple and rapid liquid-phase microextraction (LPME) method using a hollow fiber membrane (HFM) in conjunction with gas chromatography–mass spectrometry (GC–MS) is presented for the quantitative determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 organochlorine pesticides (OCPs) in rainwater samples. The LPME conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of hollow fiber exposure time, stirring rate, sample pH, and composition. Enrichment factors of more than 100 could be achieved within 35 min of extraction with relative standard deviations (R.S.D.s) 1.3–13.6% for PAHs and 1.7–13.8% for OCPs, respectively, over a wide range of analyte concentrations. Detection limits ranged from 0.002 to 0.047 μg l−1 for PAHs, and from 0.013 to 0.059 μg l−1 for OCPs, respectively. The newly developed LPME–GC–MS method has been validated for the analysis of PAHs and OCPs in rainwater samples. Extraction recoveries from spiked synthetic rainwater samples varied from 73 to 115% for PAHs and from 75 to 113% for OCPs, respectively. Real rainwater samples were analyzed using the optimized method. The concentrations of PAHs and OCPs in real rainwater samples were between 0.005–0.162, and 0.063 μg l−1, respectively.